US4451578A - Iron oxide catalyst for steam reforming - Google Patents

Iron oxide catalyst for steam reforming Download PDF

Info

Publication number
US4451578A
US4451578A US06/372,252 US37225282A US4451578A US 4451578 A US4451578 A US 4451578A US 37225282 A US37225282 A US 37225282A US 4451578 A US4451578 A US 4451578A
Authority
US
United States
Prior art keywords
iron oxide
catalyst
alumina
catalysts
steam
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Fee Related
Application number
US06/372,252
Other languages
English (en)
Inventor
Herbert J. Setzer
John A. S. Bett
Roger R. Lesieur
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
RTX Corp
Original Assignee
United Technologies Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by United Technologies Corp filed Critical United Technologies Corp
Assigned to UNITED TECHNOLOGIES CORPORATION, A CORP. OF DE. reassignment UNITED TECHNOLOGIES CORPORATION, A CORP. OF DE. ASSIGNMENT OF ASSIGNORS INTEREST. Assignors: BETT, JOHN A. S., LESIEUR, ROGER R., SETZER, HERBERT J.
Priority to US06/372,252 priority Critical patent/US4451578A/en
Priority to CA000425720A priority patent/CA1197225A/fr
Priority to GB08309930A priority patent/GB2119276B/en
Priority to ZA832670A priority patent/ZA832670B/xx
Priority to CH2082/83A priority patent/CH653571A5/de
Priority to BE0/210583A priority patent/BE896503A/fr
Priority to SE8302235A priority patent/SE453264B/sv
Priority to BR8302054A priority patent/BR8302054A/pt
Priority to DE19833314424 priority patent/DE3314424A1/de
Priority to IL68465A priority patent/IL68465A/xx
Priority to NL8301426A priority patent/NL8301426A/nl
Priority to AU13898/83A priority patent/AU551803B2/en
Priority to FR8306628A priority patent/FR2525583B1/fr
Priority to IT20748/83A priority patent/IT1161231B/it
Priority to NO831441A priority patent/NO157925C/no
Priority to DK180783A priority patent/DK159718C/da
Priority to FI831408A priority patent/FI71676C/fi
Priority to JP58074868A priority patent/JPS58199701A/ja
Priority to US06/555,269 priority patent/US4522802A/en
Publication of US4451578A publication Critical patent/US4451578A/en
Application granted granted Critical
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

Links

Images

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/83—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74—Iron group metals
    • B01J23/745—Iron
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
    • C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
    • C01B3/38—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts
    • C01B3/40—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts characterised by the catalyst
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/10—Catalysts for performing the hydrogen forming reactions
    • C01B2203/1041—Composition of the catalyst
    • C01B2203/1047—Group VIII metal catalysts
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/10—Catalysts for performing the hydrogen forming reactions
    • C01B2203/1041—Composition of the catalyst
    • C01B2203/1047—Group VIII metal catalysts
    • C01B2203/1052—Nickel or cobalt catalysts
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/10—Catalysts for performing the hydrogen forming reactions
    • C01B2203/1041—Composition of the catalyst
    • C01B2203/1047—Group VIII metal catalysts
    • C01B2203/1064—Platinum group metal catalysts
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/10—Catalysts for performing the hydrogen forming reactions
    • C01B2203/1041—Composition of the catalyst
    • C01B2203/1082—Composition of support materials
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/10—Catalysts for performing the hydrogen forming reactions
    • C01B2203/1041—Composition of the catalyst
    • C01B2203/1088—Non-supported catalysts
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/10—Catalysts for performing the hydrogen forming reactions
    • C01B2203/1041—Composition of the catalyst
    • C01B2203/1094—Promotors or activators
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/10—Process efficiency
    • Y02P20/129—Energy recovery, e.g. by cogeneration, H2recovery or pressure recovery turbines
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Definitions

  • the field of art to which this invention pertains is catalytic reforming of gaseous and/or liquid hydrocarbons utilizing the injection of steam to produce hydrogen.
  • hydrocarbon material In the production of hydrogen, it is well known in the art to treat hydrocarbon material with a catalyst at high temperatures in the presence of steam.
  • the hydrocarbon materials generally used are natural gas and naphtha which have been desulfurized to 0.1 part per million (ppm, by weight) sulfur.
  • Hydrogen, carbon monoxide and carbon dioxide are the products of the reaction. These products are often cooled and passed over a shift conversion catalyst where the carbon monoxide is further reacted with steam to produce additional hydrogen and carbon dioxide.
  • Hydrogen generators and especially hydrogen generators for fuel cell powerplants may be required to operate with heavier fuels and, in the future, coal derived liquids. These heavier distillate fuels cannot readily be desulfurized to the 0.1 ppm sulfur level that is required for the conventional steam reforming process. Direct reforming of heavier fuels without desulfurization require higher temperatures to overcome the reduction in catalytic activity in the presence of sulfur. When the commercially available nickel steam reforming catalysts are used in this fashion, carbon deposition and reactor plugging occur and reactor operation cannot be sustained. The problem of carbon formation with conventional nickel catalysts can be overcome by adding air or oxygen to the hydrocarbon/steam fuel mixture.
  • oxygen to carbon ratios (O 2 /C) equal to or greater than 0.42-0.46 carbon formation is eliminated with a 1380° F. (738° C.) preheat.
  • O 2 /C oxygen to carbon ratio
  • O 2 /C in the range of 0.35 are desirable.
  • the present invention is directed to a catalyst specifically adapted for use in autothermal and tubular stam reforming systems which substantially eliminates carbon plugging in such reforming systems and allows autothermal reformers to operate at reduced O 2 /C ratios with heavier distillate hydrocarbons such as No. 2 fuel oil.
  • Such catalysts comprise stabilized iron oxide containing at least 90% by weight iron oxide and iron oxide supported on an alumina carrier.
  • the alumina can optionally be lanthanum stabilized or calcium oxide impregnated.
  • Another aspect of the invention includes an autothermal reforming process utilizing the catalyst system according to the present invention.
  • Another aspect of this invention includes a tubular steam reforming process utilizing the catalyst system according to the present invention.
  • FIG. 1 shows regions of carbon-free steam reforming operation for various catalysts as a function of oxygen to fuel carbon ratios and reaction temperature.
  • FIG. 2 shows activity of catalyst material according to the present invention as a function of temperature.
  • the iron oxide catalysts according to the present invention can comprise either ferrous oxide or ferric oxide and in general (note the examples below) comprise a mixture of the two. If unsupported, the iron oxide contains promoters such as alumina, potassium oxide, calcium oxide and silicon dioxide in relatively small amounts, for example, up to about 2% by weight which can be added during catalyst preparation. In such instances, the iron oxide (FeO and Fe 2 O 3 ) comprises at least 90% by weight of the catalyst.
  • the supported iron oxide is generally impregnated into the alumina substrate out of aqueous solution.
  • the supported iron oxide comprises from about 10% to about 90% by weight of the catalyst plus substrate according to the present invention, and preferably comprises about 20% to about 30% by weight. Although the supported iron oxide can contain promoters or modifiers, typically it does not.
  • the substrate material either Al 2 O 3 , a lanthanum stabilized alumina or a calcium oxide impregnated alumina can be used.
  • the Al 2 O 3 pellets are typically about 0.125 inch (0.318 cm) in diameter with a average length of about 0.14 inch (0.356 cm) and are available commercially from Harshaw Chemical Co., Cleveland, Ohio (designated Al-4104E).
  • the lanthanum stabilized alumina substrate is a commercially available catalyst support material available from W. R. Grace & Co. (e.g. Grace SRDX-1/79-1).
  • the calcium oxide containing alumina is prepared by impregnating the alumina with a solution (preferably aqueous) of a calcium salt (preferably calcium nitrate) followed by drying to remove the solvent, and calcining in air to oxidize the deposited salt to calcium oxide. Calcining temperatures may vary depending on the particular salt used, but generally temperatures of about 1850° F. (1010° C.) are used, e.g. for calcium nitrate. Enough calcium salt is deposited on the support material such that after calcining about 10% to about 35% calcium is present in the support material, and preferably about 15% by weight.
  • a calcium salt preferably calcium nitrate
  • the iron oxide catalyst material according to the present invention is deposited on the substrate material by any conventional method in this art, and as stated above, preferably out of aqueous solution.
  • Metal salts and typically the nitrates are dissolved in either aqueous or organic solvents and dried on the substrate.
  • the deposited salts are then calcined to form the oxides.
  • Iron oxide on lanthanum stabilized alumina was prepared as follows: 1713 grams fo Fe(NO 3 ) 3 .9H 2 O were dissolved in 212 ml of water. This solution was used to impregnate pellets of a lanthanum stabilized alumina substrate, commercially available from W. R. Grace Corporation (Davison Division) under the designation SRDX-1/79-1. The pellets were sized similar to those of Example 1. The mixture was placed in an ultrasonic blender for 5 minutes, allowed to stand for 30 minutes and the excess solution was decanted. The catalyst was dried at 270° F. (132° C.) for 3.5 hours and then calcined at 1502° F. (817° C.) for 16 hours. The finished product weighed 980 grams.
  • a steam reforming catalyst of iron oxide on CaO containing Al 2 O 3 was prepared as follows:
  • the impregnated material was placed in an ultrasonic blender for 5 minutes and then allowed to stand for 30 minutes. The excess solution was then decanted, dried at 300° F. (149° C.) for 11/2 hours and calcined at 1850° F. (1010° C.) for 16 hours. This product weighed 426 grams. This material was then impregnated with a solution consisting of 425 grams of Fe(NO 3 ) 3 .9H 2 O dissolved in 47 ml of H 2 O.
  • the material was placed in an ultrasonic blender for 5 minutes, allowed to stand for 30 minutes and then excess solution was decanted.
  • the catalyst was dried at 290° F. (143° C.) for 3 hours and calcined at 1830° F. (999° C.) for 16 hours.
  • the impregnating with Fe(NO 3 ) 3 . 9H 2 O, blending, drying and calcining was then repeated.
  • A is a commercial nickel catalyst (25% by weight nickel on an ⁇ -alumina support material); B is the CaO on Al 2 O 3 of Example 3; and C is iron oxide on CaO impregnated Al 2 O 3 of Example 3 and D the unsupported catalyst of Example 4.
  • FIG. 2 also shows the improved performance characteristics of catalysts according to the present invention where A is the unsupported iron oxide of Example 4; B is the iron oxide on CaO impregnated alumina of Example 3; C is the iron oxide on untreated alumina; and D is the iron oxide on lanthanum stabilized alumina of Example 2.
  • the reactants were steam reformed in the isothermal tubular steam microreformer 0.305 inch (0.775 cm) inner diameter containing 1 inch (2.54 cm) in length, or 0.5 gram, of catalyst material. Ethane containing 2,225 parts per million by weight H 2 S (at about 1 atmosphere pressure) was used as the fuel.
  • reaction rate constant (K) is plotted against the reciprocal of the absolute test temperature.
  • reaction rate constant (k)(synonymous with activity) is defined by the pseudo-first order rate equation: ##EQU1##
  • Types of reformers in which the catalysts according to the present invention demonstrate the improved resistance to carbon formation are tubular reformers, autothermal reformers, adiabatic reformers and cyclic reformers.
  • the primary difference between these reformers is the manner in which heat is supplied for the endothermic reforming reaction.
  • the tubular reformer the heat is supplied through the walls of a cylinder to the catalyst material.
  • the autothermal reformer the heat is supplied to the catalyst bed directly by the heated gases entering and combusting in the reformer.
  • U.S. Pat. No. 3,967,507 the disclosure of which is incorporated by reference.
  • a plurality of reformers are operated simultaneously with one set of reformers operating under a combustion phase (reacting fuel and air) to provide the necessary heat for the hydrogen production phase and the other set of reformers operating under the hydrogen production phase (reacting hydrocarbon and steam), with a switching of phases when the temperature of the reformers in the hydrocarbon production phase drops below that necessary to sustain hydrogen production.
  • a combustion phase reacting fuel and air
  • the other set of reformers operating under the hydrogen production phase reacting hydrocarbon and steam
  • iron oxide catalysts according to the present invention can be used alone, a particularly attractive arrangement for the autothermal reformer includes the use of only an inlet portion of iron oxide catalyst according to the present invention in such reformer.
  • this inlet region all the oxygen reacts with the hydrocarbon and temperatures increase very rapidly.
  • the reactor is loaded with high activity nickel or rhodium catalysts as described in commonly assigned copending application Ser. No. 333,841, filed Dec. 23, 1981, the disclosure of which is incorporated by reference.
  • hydrocarbons and reaction intermediates react with steam. Due to the endothermic nature of the reaction with steam, temperatures drop, and it is important to have a high activity catalyst in this region.
  • Typical ratios for such multi-catalyst system areone-third of the reactor length comprising the iron oxide catalyst of the present invention and two-thirds of the reactor length comprising the high activity nickel or rhodium described above.
  • the use of such a multiple catalyst system allows greater flexibility in the maximum allowable reactor temperature and the method of introducing the air into the reactor.
  • iron oxide catalyst systems have been described as preferably supported, one may use such systems unsupported (e.g. the Katalco 35-4 iron oxide catalyst) in steam reforming processes according to the present invention if one is willing to suffer the lessened performance shown above (e.g. note FIG. 2).
  • this invention has been described in terms of alumina, calcium oxide impregnated alumina and lanthanum stabilized alumina catalyst carrier material, it is possible that similar improved results are obtainable with other promoted alumina carrier material such as magnesium oxide, magnesia and titania promoters or magnesia and titania carrier material containing no alumina as well.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Combustion & Propulsion (AREA)
  • Inorganic Chemistry (AREA)
  • Catalysts (AREA)
  • Hydrogen, Water And Hydrids (AREA)
US06/372,252 1982-04-26 1982-04-26 Iron oxide catalyst for steam reforming Expired - Fee Related US4451578A (en)

Priority Applications (19)

Application Number Priority Date Filing Date Title
US06/372,252 US4451578A (en) 1982-04-26 1982-04-26 Iron oxide catalyst for steam reforming
CA000425720A CA1197225A (fr) 1982-04-26 1983-04-12 Reformage a la vapeur sur catalyseur a l'oxyde de fer
GB08309930A GB2119276B (en) 1982-04-26 1983-04-13 Steam reforming utilizing iron oxide catalyst
ZA832670A ZA832670B (en) 1982-04-26 1983-04-15 Steam reforming utilizing iron oxide catalyst
CH2082/83A CH653571A5 (de) 1982-04-26 1983-04-19 Eisenoxidkatalysator fuer die dampfreformierung und verfahren zur dampfreformierung.
BE0/210583A BE896503A (fr) 1982-04-26 1983-04-19 Intallation et procede de reformage a la vapeur avec catalyseur a activite elevee
SE8302235A SE453264B (sv) 1982-04-26 1983-04-20 Hogaktivt katalysatorsystem samt anvendning av detsamma vid angreformering
BR8302054A BR8302054A (pt) 1982-04-26 1983-04-20 Sistema de catalisador de alta atividade para reforma com vapor d'agua,processo de reforma,auto-termica com vapor d'agua e processo de reforma tubular com vapor d'agua
DE19833314424 DE3314424A1 (de) 1982-04-26 1983-04-21 Eisenoxidkatalysator fuer die dampfreformierung und verfahren zur dampfreformierung
NL8301426A NL8301426A (nl) 1982-04-26 1983-04-22 Stoomreformeringskatalysatorsysteem met hoge activiteit, alsmede werkwijze, waarbij deze katalysator wordt toegepast.
IL68465A IL68465A (en) 1982-04-26 1983-04-22 Steam reforming iron oxide catalyst and process utilizing it
AU13898/83A AU551803B2 (en) 1982-04-26 1983-04-22 Alumina supported iron oxide steam reforming catalyst
FR8306628A FR2525583B1 (fr) 1982-04-26 1983-04-22 Installation et procede de reformage a la vapeur avec catalyseur a activite elevee
IT20748/83A IT1161231B (it) 1982-04-26 1983-04-22 Sistema di riformazione a vapore utilizzante un catalizzatore di ossido di ferro
FI831408A FI71676C (fi) 1982-04-26 1983-04-25 Aongreformation utnyttjande jaernoxidkatalysator.
DK180783A DK159718C (da) 1982-04-26 1983-04-25 Hoejaktivt katalysatorsystem til vanddampreforming og dets anvendelse
NO831441A NO157925C (no) 1982-04-26 1983-04-25 Katalysatorsystem til dampreformering samt anvendelse av samme.
JP58074868A JPS58199701A (ja) 1982-04-26 1983-04-26 水蒸気改質触媒
US06/555,269 US4522802A (en) 1982-04-26 1983-11-25 Steam reforming utilizing iron oxide catalyst

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US06/372,252 US4451578A (en) 1982-04-26 1982-04-26 Iron oxide catalyst for steam reforming

Related Child Applications (1)

Application Number Title Priority Date Filing Date
US06/555,269 Division US4522802A (en) 1982-04-26 1983-11-25 Steam reforming utilizing iron oxide catalyst

Publications (1)

Publication Number Publication Date
US4451578A true US4451578A (en) 1984-05-29

Family

ID=23467346

Family Applications (1)

Application Number Title Priority Date Filing Date
US06/372,252 Expired - Fee Related US4451578A (en) 1982-04-26 1982-04-26 Iron oxide catalyst for steam reforming

Country Status (18)

Country Link
US (1) US4451578A (fr)
JP (1) JPS58199701A (fr)
AU (1) AU551803B2 (fr)
BE (1) BE896503A (fr)
BR (1) BR8302054A (fr)
CA (1) CA1197225A (fr)
CH (1) CH653571A5 (fr)
DE (1) DE3314424A1 (fr)
DK (1) DK159718C (fr)
FI (1) FI71676C (fr)
FR (1) FR2525583B1 (fr)
GB (1) GB2119276B (fr)
IL (1) IL68465A (fr)
IT (1) IT1161231B (fr)
NL (1) NL8301426A (fr)
NO (1) NO157925C (fr)
SE (1) SE453264B (fr)
ZA (1) ZA832670B (fr)

Cited By (26)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4894297A (en) * 1988-12-07 1990-01-16 Westinghouse Electric Corp. Electrochemical generator apparatus containing modified fuel electrodes for use with hydrocarbon fuels
US4898792A (en) * 1988-12-07 1990-02-06 Westinghouse Electric Corp. Electrochemical generator apparatus containing modified high temperature insulation and coated surfaces for use with hydrocarbon fuels
US5112527A (en) * 1991-04-02 1992-05-12 Amoco Corporation Process for converting natural gas to synthesis gas
US5789339A (en) * 1995-06-07 1998-08-04 W. R. Grace & Co.-Conn. Catalyst for oxidizing oxygen-containing organic compounds in waste gas
WO2000029092A1 (fr) 1998-11-10 2000-05-25 International Fuel Cells, Llc Inhibition des depots de carbone sur les parois des reformeurs vapeur des gaz combustibles
WO2000033408A1 (fr) * 1998-11-10 2000-06-08 International Fuel Cells, Llc. Inhibition des depots de carbone sur les parois d'un reformeur a vapeur de gaz combustible
WO2000072954A1 (fr) * 1999-05-27 2000-12-07 International Fuel Cells, Llc Dispositif de reformage autothermique leger et compact
WO2000076651A1 (fr) * 1999-06-14 2000-12-21 International Fuel Cells, Llc Ensemble de reformage autothermique au carburant-methane compact et leger
US6190623B1 (en) * 1999-06-18 2001-02-20 Uop Llc Apparatus for providing a pure hydrogen stream for use with fuel cells
WO2001052978A1 (fr) * 2000-01-24 2001-07-26 International Fuel Cells, Llc Ensemble reformeur autothermique de gaz combustible
US6641795B2 (en) * 1997-10-28 2003-11-04 Ngk Insulators, Ltd. Reformer and method for operation thereof
WO2004030810A1 (fr) * 2002-10-02 2004-04-15 Yara International Asa Catalyseur pour la synthese de l'ammoniac
US6967063B2 (en) 2001-05-18 2005-11-22 The University Of Chicago Autothermal hydrodesulfurizing reforming method and catalyst
US11059030B1 (en) 2020-01-28 2021-07-13 Saudi Arabian Oil Company Catalyst compositions having enhanced acidity for bi-reforming processes
US11059720B1 (en) 2020-01-28 2021-07-13 Saudi Arabian Oil Company Catalyst carrier for dry reforming processes
US11066299B1 (en) 2020-01-28 2021-07-20 Saudi Arabian Oil Company Catalyst compositions having enhanced acidity for steam reforming processes
WO2021154759A1 (fr) * 2020-01-28 2021-08-05 Saudi Arabian Oil Company Composition de catalyseur contenant du nickel ayant une acidité améliorée pour des procédés de bi-reformage
WO2021154793A1 (fr) * 2020-01-28 2021-08-05 Saudi Arabian Oil Company Support de catalyseur pour procédés de reformage autothermique
WO2021154757A1 (fr) * 2020-01-28 2021-08-05 Saudi Arabian Oil Company Composition de catalyseur contenant du nickel ayant une acidité améliorée pour des procédés de reformage à la vapeur
WO2021154790A1 (fr) * 2020-01-28 2021-08-05 Saudi Arabian Oil Company Support de catalyseur pour procédés de reformage à la vapeur
WO2021154758A1 (fr) * 2020-01-28 2021-08-05 Saudi Arabian Oil Company Composition de catalyseur contenant du nickel ayant une acidité améliorée pour des procédés de reformage autothermique
US11247898B2 (en) 2020-01-28 2022-02-15 Saudi Arabian Oil Company Catalyst carrier for bi-reforming processes
US11338270B2 (en) 2020-01-28 2022-05-24 Saudi Arabian Oil Company Catalyst compositions having enhanced acidity for autothermal reforming processes
US11478777B2 (en) 2020-01-28 2022-10-25 Saudi Arabian Oil Company Catalyst compositions having enhanced acidity for dry reforming processes
US11498053B2 (en) 2020-01-28 2022-11-15 Saudi Arabian Oil Company Nickel-containing catalyst composition having enhanced acidity for dry reforming processes
US20230151279A1 (en) * 2019-10-09 2023-05-18 Markus Reissner Process and system for producing a hydrocarbon-containing and hydrogen-containing gas mixture from plastic

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5094222A (en) * 1989-11-17 1992-03-10 Matsushita Electric Industrial Co., Ltd. Catalytic composite and a cooker having the same
DE102013214284A1 (de) * 2013-07-22 2015-01-22 Siemens Aktiengesellschaft Speicherstruktur und Verfahren zur Herstellung

Citations (22)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US26188A (en) * 1859-11-22 Coal-hod
US2378905A (en) * 1942-01-01 1945-06-26 Houdry Process Corp Catalysis
US2666086A (en) * 1949-11-14 1954-01-12 Phillips Petroleum Co Preparation of iron dehydrogenation catalysts
US3097156A (en) * 1960-06-30 1963-07-09 Phillips Petroleum Co Process for concurrent upgrading of iron ore and heavy crude oils
US3106457A (en) * 1960-03-22 1963-10-08 Kellogg M W Co Production of hydrogen by catalytic steam reforming of hydrocarbons
US3304150A (en) * 1963-09-05 1967-02-14 Grace W R & Co Method of treating exhaust gases of internal combustion engines
USRE26188E (en) 1957-02-05 1967-04-11 Hydrocarbon conversion process
US3340011A (en) * 1963-12-16 1967-09-05 Universal Oil Prod Co Hydrogen production
US3397154A (en) * 1963-07-09 1968-08-13 Du Pont Preparation of alumina-supported catalyst compositions and the products thereof
US3437703A (en) * 1966-05-05 1969-04-08 Foster Grant Co Inc Catalytic dehydrogenation process and compositions
US3445402A (en) * 1964-12-30 1969-05-20 Catalysts & Chem Inc High temperature catalysts
US3533766A (en) * 1966-05-11 1970-10-13 Azote & Prod Chim Process for reforming hydrocarbons under high pressure
US3644216A (en) * 1963-07-24 1972-02-22 Ugine Kuhlmann Catalysts
US3644557A (en) * 1968-05-30 1972-02-22 Azote & Prod Chim Catalyst compositions for preparing ethylene
US3711426A (en) * 1970-02-26 1973-01-16 Topsoe H Process for preparing a chromium-promoted iron oxide catalyst
US3725495A (en) * 1969-12-23 1973-04-03 Toksoe H Catalytic steam cracking of hydrocarbons and catalysts therefor
US3758609A (en) * 1971-01-11 1973-09-11 Phillips Petroleum Co Processes for the oxidative dehydrogenation of hydrocarbon feedstocks
US3839229A (en) * 1971-03-17 1974-10-01 Azote & Prod Chim Ammonia-synthesis catalyst
US3867312A (en) * 1972-02-07 1975-02-18 Ethyl Corp Exhaust gas catalyst support
US4003850A (en) * 1971-10-04 1977-01-18 United States Steel Corporation Novel iron oxide catalysts
US4159968A (en) * 1976-03-24 1979-07-03 The B. F. Goodrich Company Catalyst for the preparation of ethylene and vinyl chloride from ethane
US4207211A (en) * 1975-12-08 1980-06-10 United Catalysts Inc. Catalyst for steam reforming of hydrocarbons and process of preparing the catalyst

Family Cites Families (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB924241A (en) * 1958-12-12 1963-04-24 Power Gas Ltd Improvements in or relating to the manufacture of catalysts for use in the production of combustible gases from hydrocarbons by reaction with steam
GB1107483A (en) * 1963-09-12 1968-03-27 Stazione Sperimentale Per I Co Process for production from petroleum distillates of rich gases interchangeable with natural gases
DE1542180C3 (de) * 1966-04-26 1974-08-29 Girdler-Suedchemie-Katalysator Gmbh, 8000 Muenchen Katalysatoren für die Kohlenmonoxidkonvertierung
DE1767064A1 (de) * 1968-03-27 1970-09-17 Basf Ag Katalysator fuer die Herstellung von Wasserstoff aus kohlenmonoxidhaltigen Gasen
GB1259381A (fr) * 1969-03-06 1972-01-05
US4025457A (en) * 1970-09-04 1977-05-24 Toyo Engineering Corporation Process for manufacturing gaseous mixtures rich in hydrogen
FR2186452A2 (en) * 1972-05-31 1974-01-11 Azote & Prod Chim Low-porosity catalysts for ethylene prodn - by steam reforming, contains refractory oxides, rare earth oxides and group VIII metal oxides
FR2187408A1 (en) * 1972-06-06 1974-01-18 Azote & Prod Chim Steam reforming catalysts for ethylene prodn - with thermally conductive support to reduce temp gradients
GB1480337A (en) * 1973-07-24 1977-07-20 Davy Powergas Ltd Fuel gas production and catalyst therefor
US4040982A (en) * 1976-01-12 1977-08-09 Nalco Chemical Company Ozonization catalyst
JPS5311893A (en) * 1976-07-20 1978-02-02 Fujimi Kenmazai Kougiyou Kk Catalysts
GB1527955A (en) * 1977-02-25 1978-10-11 Mitsui Shipbuilding Eng Catalyst and process for gasification of hydrocarbons
JPS5443205A (en) * 1977-09-13 1979-04-05 Mitsui Eng & Shipbuild Co Ltd Liquefaction of hydrocarbons
JPS5951336B2 (ja) * 1979-03-22 1984-12-13 日本鉱業株式会社 重質炭化水素の処理用触媒
JPS5837353B2 (ja) * 1979-09-29 1983-08-16 重質油対策技術研究組合 重質油の分解軽質化と水素の製造方法
GB2085314B (en) * 1980-10-07 1984-09-12 Ici Plc Hydrocarbon cracking process and catalyst
EP0062410B1 (fr) * 1981-03-26 1986-01-22 Imperial Chemical Industries Plc Préparation catalytique d'hydrogène à partir de monoxyde de carbone et d'eau
JPS5891002A (ja) * 1981-11-24 1983-05-30 Japan Steel Works Ltd:The 重質油の流動接触部分酸化によるガス化方法

Patent Citations (22)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US26188A (en) * 1859-11-22 Coal-hod
US2378905A (en) * 1942-01-01 1945-06-26 Houdry Process Corp Catalysis
US2666086A (en) * 1949-11-14 1954-01-12 Phillips Petroleum Co Preparation of iron dehydrogenation catalysts
USRE26188E (en) 1957-02-05 1967-04-11 Hydrocarbon conversion process
US3106457A (en) * 1960-03-22 1963-10-08 Kellogg M W Co Production of hydrogen by catalytic steam reforming of hydrocarbons
US3097156A (en) * 1960-06-30 1963-07-09 Phillips Petroleum Co Process for concurrent upgrading of iron ore and heavy crude oils
US3397154A (en) * 1963-07-09 1968-08-13 Du Pont Preparation of alumina-supported catalyst compositions and the products thereof
US3644216A (en) * 1963-07-24 1972-02-22 Ugine Kuhlmann Catalysts
US3304150A (en) * 1963-09-05 1967-02-14 Grace W R & Co Method of treating exhaust gases of internal combustion engines
US3340011A (en) * 1963-12-16 1967-09-05 Universal Oil Prod Co Hydrogen production
US3445402A (en) * 1964-12-30 1969-05-20 Catalysts & Chem Inc High temperature catalysts
US3437703A (en) * 1966-05-05 1969-04-08 Foster Grant Co Inc Catalytic dehydrogenation process and compositions
US3533766A (en) * 1966-05-11 1970-10-13 Azote & Prod Chim Process for reforming hydrocarbons under high pressure
US3644557A (en) * 1968-05-30 1972-02-22 Azote & Prod Chim Catalyst compositions for preparing ethylene
US3725495A (en) * 1969-12-23 1973-04-03 Toksoe H Catalytic steam cracking of hydrocarbons and catalysts therefor
US3711426A (en) * 1970-02-26 1973-01-16 Topsoe H Process for preparing a chromium-promoted iron oxide catalyst
US3758609A (en) * 1971-01-11 1973-09-11 Phillips Petroleum Co Processes for the oxidative dehydrogenation of hydrocarbon feedstocks
US3839229A (en) * 1971-03-17 1974-10-01 Azote & Prod Chim Ammonia-synthesis catalyst
US4003850A (en) * 1971-10-04 1977-01-18 United States Steel Corporation Novel iron oxide catalysts
US3867312A (en) * 1972-02-07 1975-02-18 Ethyl Corp Exhaust gas catalyst support
US4207211A (en) * 1975-12-08 1980-06-10 United Catalysts Inc. Catalyst for steam reforming of hydrocarbons and process of preparing the catalyst
US4159968A (en) * 1976-03-24 1979-07-03 The B. F. Goodrich Company Catalyst for the preparation of ethylene and vinyl chloride from ethane

Cited By (40)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4894297A (en) * 1988-12-07 1990-01-16 Westinghouse Electric Corp. Electrochemical generator apparatus containing modified fuel electrodes for use with hydrocarbon fuels
US4898792A (en) * 1988-12-07 1990-02-06 Westinghouse Electric Corp. Electrochemical generator apparatus containing modified high temperature insulation and coated surfaces for use with hydrocarbon fuels
US5112527A (en) * 1991-04-02 1992-05-12 Amoco Corporation Process for converting natural gas to synthesis gas
US5789339A (en) * 1995-06-07 1998-08-04 W. R. Grace & Co.-Conn. Catalyst for oxidizing oxygen-containing organic compounds in waste gas
US5882616A (en) * 1995-06-07 1999-03-16 Megtec Systems, Inc. Catalyst and method for oxidizing oxygen-containing organic compounds in waste gas
US6641795B2 (en) * 1997-10-28 2003-11-04 Ngk Insulators, Ltd. Reformer and method for operation thereof
JP2002531363A (ja) * 1998-11-10 2002-09-24 インターナショナル フュエル セルズ，エルエルシー 燃料気体の水蒸気改質装置の壁への炭素沈積の抑制
US6120926A (en) * 1998-11-10 2000-09-19 International Fuel Cells, Llc Inhibition of carbon deposition on fuel gas steam reformer walls
WO2000033408A1 (fr) * 1998-11-10 2000-06-08 International Fuel Cells, Llc. Inhibition des depots de carbone sur les parois d'un reformeur a vapeur de gaz combustible
KR100599893B1 (ko) * 1998-11-10 2006-07-13 유티씨 퓨얼 셀즈, 엘엘씨 연료 가스 증기 개질기 벽에서의 탄소 침착 억제법
WO2000029092A1 (fr) 1998-11-10 2000-05-25 International Fuel Cells, Llc Inhibition des depots de carbone sur les parois des reformeurs vapeur des gaz combustibles
KR100599892B1 (ko) * 1998-11-10 2006-07-13 유티씨 퓨얼 셀즈, 엘엘씨 연료 가스 증기 개질기 벽에서의 탄소 침착 억제법
WO2000072954A1 (fr) * 1999-05-27 2000-12-07 International Fuel Cells, Llc Dispositif de reformage autothermique leger et compact
US6969411B2 (en) * 1999-05-27 2005-11-29 Utc Fuel Cells, Llc Compact light weight autothermal reformer assembly
US6797244B1 (en) * 1999-05-27 2004-09-28 Dtc Fuel Cells Llc Compact light weight autothermal reformer assembly
US20050072048A1 (en) * 1999-05-27 2005-04-07 Lesieur Roger R. Compact light weight autothermal reformer assembly
WO2000076651A1 (fr) * 1999-06-14 2000-12-21 International Fuel Cells, Llc Ensemble de reformage autothermique au carburant-methane compact et leger
US6746650B1 (en) * 1999-06-14 2004-06-08 Utc Fuel Cells, Llc Compact, light weight methanol fuel gas autothermal reformer assembly
US6190623B1 (en) * 1999-06-18 2001-02-20 Uop Llc Apparatus for providing a pure hydrogen stream for use with fuel cells
WO2001052978A1 (fr) * 2000-01-24 2001-07-26 International Fuel Cells, Llc Ensemble reformeur autothermique de gaz combustible
US6967063B2 (en) 2001-05-18 2005-11-22 The University Of Chicago Autothermal hydrodesulfurizing reforming method and catalyst
WO2004030810A1 (fr) * 2002-10-02 2004-04-15 Yara International Asa Catalyseur pour la synthese de l'ammoniac
US20230151279A1 (en) * 2019-10-09 2023-05-18 Markus Reissner Process and system for producing a hydrocarbon-containing and hydrogen-containing gas mixture from plastic
WO2021154758A1 (fr) * 2020-01-28 2021-08-05 Saudi Arabian Oil Company Composition de catalyseur contenant du nickel ayant une acidité améliorée pour des procédés de reformage autothermique
US11247898B2 (en) 2020-01-28 2022-02-15 Saudi Arabian Oil Company Catalyst carrier for bi-reforming processes
WO2021154759A1 (fr) * 2020-01-28 2021-08-05 Saudi Arabian Oil Company Composition de catalyseur contenant du nickel ayant une acidité améliorée pour des procédés de bi-reformage
WO2021154793A1 (fr) * 2020-01-28 2021-08-05 Saudi Arabian Oil Company Support de catalyseur pour procédés de reformage autothermique
WO2021154757A1 (fr) * 2020-01-28 2021-08-05 Saudi Arabian Oil Company Composition de catalyseur contenant du nickel ayant une acidité améliorée pour des procédés de reformage à la vapeur
WO2021154790A1 (fr) * 2020-01-28 2021-08-05 Saudi Arabian Oil Company Support de catalyseur pour procédés de reformage à la vapeur
US11059720B1 (en) 2020-01-28 2021-07-13 Saudi Arabian Oil Company Catalyst carrier for dry reforming processes
US11242246B2 (en) 2020-01-28 2022-02-08 Saudi Arabian Oil Company Catalyst carrier for autothermal reforming processes
US11242245B2 (en) 2020-01-28 2022-02-08 Saudi Arabian Oil Company Catalyst carrier for steam reforming processes
US11066299B1 (en) 2020-01-28 2021-07-20 Saudi Arabian Oil Company Catalyst compositions having enhanced acidity for steam reforming processes
US11286160B2 (en) 2020-01-28 2022-03-29 Saudi Arabian Oil Company Nickel-containing catalyst composition having enhanced acidity for autothermal reforming processes
US11338270B2 (en) 2020-01-28 2022-05-24 Saudi Arabian Oil Company Catalyst compositions having enhanced acidity for autothermal reforming processes
US11365120B2 (en) 2020-01-28 2022-06-21 Saudi Arabian Oil Company Nickel-containing catalyst composition having enhanced acidity for steam reforming processes
US11396006B2 (en) 2020-01-28 2022-07-26 Saudi Arabian Oil Company Nickel-containing catalyst composition having enhanced acidity for bi-reforming processes
US11478777B2 (en) 2020-01-28 2022-10-25 Saudi Arabian Oil Company Catalyst compositions having enhanced acidity for dry reforming processes
US11498053B2 (en) 2020-01-28 2022-11-15 Saudi Arabian Oil Company Nickel-containing catalyst composition having enhanced acidity for dry reforming processes
US11059030B1 (en) 2020-01-28 2021-07-13 Saudi Arabian Oil Company Catalyst compositions having enhanced acidity for bi-reforming processes

Also Published As

Publication number Publication date
GB8309930D0 (en) 1983-05-18
AU551803B2 (en) 1986-05-08
DK180783D0 (da) 1983-04-25
FI831408L (fi) 1983-10-27
SE453264B (sv) 1988-01-25
GB2119276B (en) 1986-07-16
IT1161231B (it) 1987-03-18
ZA832670B (en) 1983-12-28
FI71676B (fi) 1986-10-31
SE8302235L (sv) 1983-10-27
SE8302235D0 (sv) 1983-04-20
NL8301426A (nl) 1983-11-16
DK159718C (da) 1991-04-22
IL68465A0 (en) 1983-07-31
FI831408A0 (fi) 1983-04-25
BE896503A (fr) 1983-08-16
JPH0413025B2 (fr) 1992-03-06
DE3314424A1 (de) 1983-11-10
CH653571A5 (de) 1986-01-15
GB2119276A (en) 1983-11-16
NO157925C (no) 1988-06-15
FI71676C (fi) 1987-02-09
NO831441L (no) 1983-10-27
DK159718B (da) 1990-11-26
NO157925B (no) 1988-03-07
IT8320748A0 (it) 1983-04-22
IL68465A (en) 1986-09-30
FR2525583A1 (fr) 1983-10-28
DE3314424C2 (fr) 1991-10-17
FR2525583B1 (fr) 1988-04-01
JPS58199701A (ja) 1983-11-21
DK180783A (da) 1983-10-27
AU1389883A (en) 1983-11-03
BR8302054A (pt) 1983-12-27
CA1197225A (fr) 1985-11-26

Similar Documents

Publication Publication Date Title
US4451578A (en) Iron oxide catalyst for steam reforming
US4415484A (en) Autothermal reforming catalyst
US4844837A (en) Catalytic partial oxidation process
US3186797A (en) Process for catalytically steam reforming hydrocarbons
US4693882A (en) Steam reforming utilizing sulfur tolerant catalyst
US4522802A (en) Steam reforming utilizing iron oxide catalyst
US5023276A (en) Preparation of normally liquid hydrocarbons and a synthesis gas to make the same, from a normally gaseous hydrocarbon feed
US4755498A (en) Steam reforming catalyst
US4863707A (en) Method of ammonia production
US4483691A (en) Production of synthetic natural gas from coal gasification liquid by-products
EP1481729B1 (fr) Procédé autothermique de réformage à la vapeur d'une charge d'hydrocabures
US4473543A (en) Autothermal reforming catalyst and process
US4087259A (en) Process for partially oxidizing hydrocarbons
US3451949A (en) Catalyst for reforming hydrocarbons
US5752995A (en) Catalyst and process for the production of hydrogen and/or methane
DK163294B (da) Fremgangsmaade til fremstilling af en hydrogenrig gas ved autotermal reformering
JP2010524684A (ja) 天然ガスを高級炭素化合物に転換するための触媒および方法
CA2130953C (fr) Procede de reformage a la vapeur des hydrocarbures
US3945944A (en) Catalyst for the production of hydrogen and/or methane
US4321250A (en) Rhodium-containing perovskite-type catalysts
US20050238574A1 (en) High performance water gas shift catalyst and a method of preparing the same
US4414140A (en) Catalyst for steam reforming
US4503029A (en) Steam reforming utilizing high activity catalyst
US3466159A (en) Process and catalyst for production of methane-rich gas
JPS62262746A (ja) 蒸気改質用触媒

Legal Events

Date Code Title Description
AS Assignment

Owner name: UNITED TECHNOLOGIES CORPORATION; HARTFORD, CT. A

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNORS:SETZER, HERBERT J.;BETT, JOHN A. S.;LESIEUR, ROGER R.;REEL/FRAME:003989/0687

Effective date: 19820420

FPAY Fee payment

Year of fee payment: 4

FPAY Fee payment

Year of fee payment: 8

REMI Maintenance fee reminder mailed
LAPS Lapse for failure to pay maintenance fees
FP Lapsed due to failure to pay maintenance fee

Effective date: 19960529

STCH Information on status: patent discontinuation

Free format text: PATENT EXPIRED DUE TO NONPAYMENT OF MAINTENANCE FEES UNDER 37 CFR 1.362